Siloxane polymers for soil-repellent and soil-release textile finishes

ABSTRACT

FLUOROCARBON SILANES ARE COPOLYMERIZED WITH SILANES WHICH CONTAIN TWO OR MORE ALKYLENEOXY GROUPS. THE COPOLYMERS ARE USEFUL FOR APPLICATION TO FIBROUS MATERIALS TO PROVIDE BOTH SOIL REPELLENCY AND SOIL RELEASABILITY

United States Patent Office US. Cl. zen-443.2 B 2 Claims ABSTRACT on THEDISCLOSURE Fluorocarbon silanes are copolymerized with silanes whichcontain two or more alkyleneoxy groups. The cpolymers are useful forapplication to fibrous materials to provide both soil repellency andsoil releasability.

This application is a division of our co-pending application Ser. No.157,759, filed June 28, 1971, now Pat. 3,809,783, which in turn is adivision of Ser. No. 38,899, filed May 19, 1970, now Pat. 3,639,156. k Anon-exclusive, irrevocable,royalty-free license in the invention hereindescribed, throughout the world for all purposes of the United StatesGovernment, with the power to grant sublicenses for such purposes, ishereby granted to the Government of the United States of America.

This invention relates to and has among its objects the provision ofnovel polymers which are particularly useful for impartingsoil-repellent and soil-release properties to fibrous materials. Theobjects of the invention also include procedures for-treating fibrousmaterials with the polymers, and the treated materials as new articlesof manufacture. Further objects of the invention will be evident tromthe following description wherein parts and percentages are by weightunless otherwise specified.

It is not generally realized that maintaining textiles in a cleanstate-involves two difierent properties of the textile. One is soilrepellency, that is, the ability of the textile to resist staining whenit is contacted with gravy, butter, grease, or other oily substances.The other is soil releasability. Assuming that a textile has becomestained, this property concerns the ease or difiiculty of washing outthe stains. The soil repellency and soil releasability characteristicsof a given textile depend on the kind of fiber from which it is made andthe kind of finishing agent which has been applied to it. Natural fiberssuch as cotton and wool exhibit little soil repellency, but on the otherhand when they do become soiled they are readily cleaned, that is, theyexhibit a high level of soil releasability. Some of the synthetics,notably polyesters, not only exhibit a low level of soil repellency butalso a low level of soil releasability. Thus, the modern trend towardfabricating textiles from blends of cotton or wool with polyesters hasaggravated the situation because such blends are easily soiled and theabsorbed soil is difficult to wash out. The application of'resins forproviding durable-press properties still further aggravates the soilrelease situation. Al-

most everyone has encountered a situation where a socalledwash-and-we'argarment of resin-treated cotton/ polyester orwool/polyester blended material has become soiled by contact with anoily substance, and it is found that it takes repeated washings toremove the stains. In.

eiforts to circumvent 'these problems, fluorocarbon polymers have beenapplied to the textiles. Because of the oleophobic properties of mostfluorocarbons, such treatments do enhance the soil. repellence ofthefabric. However, they tend to make the soil release properties even Hworse because the aqueous washing medium cannot prop- 3,828,087 PatentedAug. 6, 1974 erly wet the fabric, hence cannot remove stains. Anotherremedy has been to apply hydrophilic materials, generally polymeric, tothe textiles. These generally make it easier to wash out stains, butthey do not enhance the ability of the textile to resist staining whencontacted with oily substances.

A particular object of the invention is to provide the means foralleviating the problems outlined above. The invention provides polymerswhich confer oil repellence on fabrics so that they strongly resiststaining, e.g., by oily foods or the like. concomitantly, these polymersconfer soil-release properties on the fabric to which they are applied.This means that if the fabric does become stained, the stains can bereadily washed out. Another advantage is that these polymers conferanti-static properties on the fabric to which they are applied.

The polymers having this desirable combination of properties arecopolymerization products of at least two different monomers, oneimparting oleophobic properties, the other hydrophilic properties. Morespecifically, the oleophobic monomer is a silane which contains aterminal perfluoroalkyl group of 3 to 18 perfluorinated carbon atoms,such group being hereinafter designated as R,. The hydrophilic monomeris a silane which contains two or more groups of the structure AlkOwherein Alk is an alkylene group containing 2 to 6 carbon atoms. Theresulting siloxane copolymers have a silicon-to-oxygen backbone, pluspendant R, groups which provide oleophobicity, and groups of thestructure Alk-O which provide hydrophilicity. The monomers are describedfurther in the following paragraphs.

THE OLEOPHOBIC MONOMER Genetically, the oleophobic monomer used inaccordance with the invention has the structure wherein:

R, is a perfluoroalkyl group containing 3 to 18 perfluor inated carbonatoms. This perfluoroalkyl group can be of an open-chain (acyclic)configuration, straight or branched. Alternatively, it may be of acyclic structure such as a perfluorocyclohexyl group, or it may be acombination of acyclic and cyclic structures. Generally, the acyclicstructures are preferred.

Z is a divalent bridging group linked to a carbon of R, and a carbon of(CH,,),,, such as an ester (C0 or -SO;,-), an ether (-0-, (CH O-, or--S), an amine (-(CH NR'), or an amide group, wherein s is an integerfrom 1 to 6 and R' is hydrogen or a lower alkyl radical. I

R is a member of the group consisting of hydrogen, monovalenthydrocarbon radicals,- and monovalent halohydrocarbon radicals. Examplesof R are hydrogen: an alkyl radical such as methyl, ethyl, isopropyl,butyl, cyclohexyl, dodecyl, etc.; an aryl radical such as phenyl, tolyl,ethylphenyl, .is'opropylphenyl, 'xylyl, xenyl, naphthyl, etc.; anaralkyl radical such as benzyl or 2-phenylethyl; or a halogenatedhydrocarbon radical such as 2- chloro, trifluoromethyl, 3 chloropropyl,2,2,2 trifiuoroethyl, 4-chloro- (or fiuoro-) eyclohexyl, p-chloro- (orbromoor fluoro-') phenyl, and the like; 4

Y is a member of the group consisting of halogen, alkoxy, aroxy, andacyloxy For example, Y may be a halogen such as fluorine, chlorine,bromine, or iodine; an alkoxy radical such. as .methoxy, .ethoxy,propoxy, isopropoxy, butoxy, cyclohexyloxy, or the like; an aroxy rradical such as phenoy, toloxy, ethylphenoxy, isopropylphenoxy, or thelike, or an acyloxy radical such as acetoxy,

propionoxy, butyroxy, or the like.

a is an integer from to 1.

b is an integer from 1 to 12.

n is an integer from 1 to 2.

p is an integer from 1 to 3.

q is an integer from 0 to 2, and the sum of n, p, and q is 4.

In the preferred compounds there is more than one hydrolyzable group(Y), i.e., p has the value 2 or 3.

These monomers are known in the art and described in the literature, forexample, in Pats. 3,012,006, 3,422,131, and 3,423,234. Examples ofindividual monomers are given below by way of illustration, notlimitation:

Of particular interest arethe monomers wherein R, is theheptafiuoroisopropyl radical since this group provides a degree ofoleophobicity equivalent to 6 or 7 fluorinated carbons in a straightchain. Monomers of this category are disclosed in our Pat. 3,422,131 andinclude compounds of the structure 1 (CF|)zCF-0-(CH:)m-Si wherein:

m is an integer from 2 to 3, and the other symbols are as in Formula I,namely: I v

R is a member of the group consisting of hydrogen, monovalenthydrocarbon radicals, and monovalent halohydrocarbon radicals.

Y is a member of the group consisting of halogen, alkoxy, aroxy, andacyloxy.

n is an integer from 1 to 2. p is an integer from 1 to 3. q is aninteger from 0 to 2, and the sum of n, p, and q is 4.

Examples of individual monomers in this sub-category are listed below byway of illustration, not limitation:

on),or-o-om-cn -ongsitom)(cum: I

; THE HYDROPHILIC MONOMER 'One category'd'f hydrophilic monomers used inac cordance with the inventionhas the structure (III) Bu u-o-mm-pg-nu-sK Yd wherein: 1

R" is a monovalent hydrocarbon radical containing 1 to 20 carbon atomsand which may be in an alkyl, aryl, or aralkyl configuration. Thenatureof the hydrocarbon substituent R" is of no criticality; it simplyserves as an inert terminator of the alkyleneoxychain.

Alk is an alkylene group containing 2 to 6 carbon atoms.

x is an integer from 2 to-10 0.

R'" is a divalent linking radical selected from the group consisting of--CH CH -CH Y c is an integer from 0 to 2. p i

d is an integer from 1 to 3, and the sum of c and d is 3. v

The remaining symbols R- and Y'are as in Formula I, namely:

R is a member of the group consisting of hydrogen, monovalenthydrocarbon radicals, and monovalent halohydrocarbon radicals.

Y is a member of the group consisting of halogen, alkoxy, aroxy, andacyloxy. 1

In the preferred monomers, there is more than one hydrolyzable group(Y), that is,'d has'the value 2 or 3.

The aforesaid hydrophilic monomers maybe readily prepared byconventional methods. A typical procedure is to start with amonoetherified polyalkyleneoxy glycol I 3 Ya wherein R, Y, c, and d areas above defined. The reaction is generally carried out'in the presenceof a catalyst such as chloroplatinic acid and results in addition of thesilane to the unsaturated group of the allyl (or methallyl ether). Thesynthesis is illustrated bythe following'equations:

In the event that a methallyl halide is used in the first Where it isdesired 'tolproduce monomers containing an ester linkage (i.e., where R'is COCH (CH or -COC(CH the synthesis is varied in the first step byesterifying'the mon'oetherified polyethyleneoxy y' o 'j R"O -(Alk) -Hwith acryloyl (or methacryloyl) chloride. In the next step, ahydrogen-containing silane is added to the intermediate as previouslydescribed; The synthesis is illustrated by the following formulas:

acryloyl chloride ought'm-om-o-c o-ini siola 5 Another category ofhydrophilic monomers used in accordance with the invention contains twosilyl groups, and has the structure wherein R, Y, R', Alk, x, c, and dare as defined in Formula 'III; 0 is an integer from 0 to 2, d is aninteger from 1 to 3, and the sum of c and d is 3. R"" is analogous to Rin that it is a member of the group consisting of In preparing thecompounds shown in Formula IV the same procedures are applied asaforesaid except that the starting material is a polyoxyalkylene glycolcontaining two terminal hydroxyls. The synthesis is illustrated asfollows:

allyl bromide CHrCH=CHg Examples of individual monomers are providedbelow by way of illustration:

Many of the polyoxyalkylene glycols available in commerce are mixturesof congeners with difiering numbers of alkyleneoxy units. Suchcommercial mixtures are suitable as starting materials for the synthesesof the hydrophilic monomers (both those of Formula III and Formula IV).Among such mixtures are those wherein the average number of alkyleneoxyunits is 2, 4, 6, 8, 10, 12, 14, 16, 20, 24, 30, or 40, for example.

PREPARATION OF THE COPOLYMERS The copolymers of the invention areprepared by conventional polymerizations used in preparing siloxanepolymers. This involves subjecting a mixture of the oleophobic andhydrophilic monomers to hydrolysis. For example, the monomer mixture isstirred with an excess of water, and then water and by-products areremoved by evaporation. A preferred technique involves dissolving themonomer mixture in a solvent such as acetone, p-dioxane,tetrahydrofuran, or other volatile solvent which is at least partlymiscible with water, and adding water to this solution with stirring.The reaction mixture is then subjected to evaporation, preferably undervacuum, to remove solvent, water, and by-products of the hydrolyticpolymerization.

The copolymers are generally viscous liquids which are soluble in mostorganic solvents, particularly fluorinatcd solvents such asbenzotrifluoride, trichlorotrifluoroethane,l,3-bis-trifluoromethylbenzene, and the like. These polymer solutionsare useful for treating fibrous materials to provide them with both soilrepellency and soil releasability.

The structure of the copolymers will vary depending on the nature of themonomers selected. For example, where the monomer of Formula I iscopolymerized with the monomer of Formula III, the copolymer willcontain repeating units of the structure R m a 2 (an Sr 1- l 2b I andrepeating units of the structure r v r R :8 Where the hydrophilicmonomer ..sclccted..ifi @QQQIding to Formula IV, the copolymerwill'containhepeatin'g units as shown in Formula V and repeatingunits ofthe structure 2 '7 n: :I As noted hereinabove, we prefer to use monornrs(both oleophobic and hydrophilic) wherein each contains at least 2hydrolyzable groups per silicyl group. Such monomers yield copolymersofgreater molecular Weight and which are capable of furtherpolymerizationfor example, after they are applied to afibrous materialand subjected to a curing operation. The monomers containing a singlehydrolyzable' group are preferably used where it may be desired to limitthe degree ofpolymerization and thus they may be used in conjunctionwith dior trifunctional monomers to act as chain stoppers.

In preparing the copolymers'of the inviitionf the "proportions of themonomers' 'may' be varied-depending on such factors as the number ofper-fiuorinated carbon atoms in the oleophobic monomerQthe numberofalkyleneoxy groups in the hydrophilic monomer, and the propertiesdesired in the copolymer. In general, the monomers are used in the ratioof about from 0.=1'td 3 molesofthe hydrophilic monomer per mole of the.oleophobiemonomer, with the proviso that the copolymer contain at least10% fluorine by weighti i I The copolymers of the invention encompassthose which are prepared by copolymerization of the oleophobic andhydrophilic monomers as above described plus one or more monomers whichare dilferent from both of the basic reactants. The additional monomermay be employed to modify the mechanical properties of *;the copolymerwithout materially afiecting its'abilityto provide soil repellency andsoil releasabilit'y, or to increase the adherence of the copolymer tofibrous substrates. Typically, the additional monomer may be di-, ortrifunctionalsilanes such as methyldichlorosilane,.dimethyldichlorosilane, methyltrichlorosilane, trichlorosilane,phenyldichlorosilane, trimethoxysilane, or the like.

TREATMENT OF FIBROUS SllBSTRATES The copolymers described herein areparticularly useful for the treatment of fibrous'materials, [such astextiles, to provide them with oil-,waten, and soil-repellency andfurther to improve their soil or stain release characteristics. Inpracticing this phase of the invention, a copolymer is prepared asdescribedabove applied to the fibrous substrate. Typically; thecopolymer is dispersed in a liquid carrier and in this form applied tothe fibrous material. The term dispersion is used in a generic sense toinclude solutions, suspensions, and emulsions. Where the copolymer is tobe applied in theform of a solution, it is dissolved in an inertvolatile solvent, e.g., benzotrifluoride, 1,3-bis-trifiuoromethylbenzene, or trichlorotrifluoroethane. Alternatively, thecopolymer isemulsified in water, with the aid of a conventional emulsifying agent.In any event, the resulting dispersion is applied to the fibrousmaterial by a conventional dip and pad technique. By varying theconcentration'of the copolymer in the dispersion and the degree ofpadding, the amount of copolymer deposited on the material may bevaried. Typically, the amount of copolymer maybe from 0.1 to 20%, basedon the weight of'lfibrous, material-but itis obvious that higher orlower proportions can be used if desired. Usually, in treating textilessuch as fabrics, the amount of copolymer is limited to about 0.1 to, 5%to attain the desired repellency'without imerrerenc wiur the hand of thetextile.

After application of, the copolymer dispersion, the treated fibroussubstrate;is subjectedto. a conventional curing operation in order tobond the polymer to the fibers. As an example of such treatment, thefibrous material is heated in the range of about 50 to 150 C. for aperiod of to 60minutes. The solvent (from the copolymer dispersion) maybe evaporated in a separate step 'prior to curing or it may simply beevaporated during the curing operation. In this curing operation theuncondensed or unhydrolyzed groups in the uncured copolymer (e.g., halo,alkoxy, or aroxy groups attached to Si) react with reactive sites in thefibers, particularly sites which contain active hydrogen as in hydroxyl,primary' and secondary amide, thiol, carboxyl, and like groups. anytypes of fibers-for example: wool, silk, hair, and other proteinousfibers; cotton, rayons, and other cellulosic fibers; nylon,polyurethane, and polyurea fibers-contain groups of this kind andtherefore are particularly suitable substrates to obtain good bonding ofthe copolymer deposit. Moreover, virtually all fibrous materials, eveninorganic products such as asbestos and glass fibers, contain moistureand during the curing operation this moisture promotes additionalhydrolysis and condensation of unreacted Si-bonded halo, alkoxy, oraroxy groups with the end result that additional, in situ,polymerization occurs so that the copolymer is durably fixed to thetreated substrate.

If it is desired to expedite the curing operation, a conventional curingcatalyst may be added to the polymer solution before application to thefibrous substrate or the catalyst may be separately deposited on thesubstrate before or after application of the copolymer dispersion.Typically, one may use such catalysts as zinc octoate, dibutyltindiacetate or dilaurate, triethanolamine titanate, triethanolaminezirconate, zirconium acetate, zirconium oxychloride, zirconium ortitanium esters of alkanols such as tetrabutyl titanate, zincperfiuorobutyrate, etc.

Fibrous materials treated with the copolymers of the invention displayan enhanced resistance to becoming soiled and if they do become stainedthey can be readily cleaned. Moreover, these advantages are attainedwithout detriment to "other properties of the textile. In particular,the treatment-does not impair the hand of the textile. In fact, the handis usually improved in that the textile is softer and moresupple.'Another point is that the improvements rendered by the processare durablethey are retained despite laundering and dry-cleaning of theproduct.

The invention may be utilized for improving the properties of all typesof fibrous materials, for example, paper; cottonflinen; hemp; jute;ramie; sisal; cellulose acetate rayons; cellulose acetate-butyraterayons; saponified acetate"rayons; viscose rayons; cuprammonium rayons;ethyl cellulose; fibers prepared from amylose, algins, or pectins; wool;silk; animal hair; mohair; leather; fur; regenerated protein fibersprepared from casein, soybean, peanut proteins, zein, gluten, eggalbumin, collagen, or keratins;

The invention is further demonstrated by the following examples whichare provided by way of illustration, not limitation.

Test Methods The tests referred to in the examples Were carried out asdescribed below:

Oil repellency.The test used was the AATCC Test Method 118-1966T.Ratings are from 0 to 8 with the higher values signifying the greaterresistance to oil penetration. In particular, the 0il-repellency ratingis the highest-numbered test liquid which will not wet the fabric inwithin a period of 30 seconds. The liquids and their correspondingnumbers are:

No. Composition 1 Nujol. 2 :35 Nujol and n-hexadecane, by vol. 3 ln-Hexadecane.

4 n-Tetradecane.

5 n-Dodecane.

6 n-Decane.

7 n-Octane. 8 n-Heptane.

Stain release.-Samples of the fabrics are stained with mineral oil, thenwashed and rated for stain release according to AATCC Test Method -1969.Residual stain is rated on a scale from 5 to 1 by comparison with astandard stain release replica which displays a graduated series ofstains. The highest number (5) indicates complete stain removal, whereasthe lowest (1) indicates virtually no stain removal.

The following oleophobic monomers were prepared by known methods:

Code desig- Monomer nation Preparation 3)2CFO(C 2)3 siC13 A Patent3,422,131.

(3H8 B Do. (CF3)2CF-O(CH) 3 'SlC12 CFa-(CF2)fl-OHg'O''(cH2)3slCl3 0Patent 3,012,006.

The following hydrophilic monomers were prepared as described inExamples 1-5 Example 1.-Preparation of Monomer D Into a dry 1-liter,B-necked flask, equipped with a stirrer, N inlet, dropping funnel andcondenser, was placed 200 ml. of dry p-dioxane and 48 g. of 50% activesodium hydride (1 mole NaH) dispersed in mineral oil. To this was addedslowly, under N 120 g. (1 mole) of the rnonomethyl ether of diethyleneglycol.

Following this, 1 mole of allyl bromide, diluted with 100 ml. ofp'dioxane, was added dropwise with stirring. The flask was cooled withice water during the addition as considerable heat was evolved. Sodiumbromide was seen to precipitate from. the mixture during the addition.\After all the allyl bromide had been added, the reaction mixture wasstirred overnight at room temperature. The reaction mixture was thenfiltered free from NaBr (111 g. solid obtained), and the filtratetreated by first distilling off the dioxane at about 100 C. atatmospheric pressure and then distilling the product under vacuum.Seventy-eight grams of the allyl ether were obtained by distillation atabout 73 C. at 5 mm. Hg pressure.

[Monomer D was then prepared from the allyl ether as follows: Threesmall, dry, Pyrex tubes sealed at one end were each charged with 2.8 g.of the allyl ether, 0.05 ml. t-butyl perbenzoate, and 3.1 ml. Cl SiH.The tubes were cooled in a Dry-'Ice bath, evacuated, sealed, and placedin a steam bath overnight. The contents of the tubes were then combinedand distilled under vacuum to yield 10.4 g. of Monomer D, b.p. 115-1l6C. at approximately 1 mm. Hg.

Example 2.-Preparation of ,Monomer E CH O( CH CH O) -(CH siCl (g isapproximately 12) This monomer was prepared in a manner similar to thatdescribed in Example 1, using (for the preparation of the allyl ether)the following materials:

225 g. of CH -O-(CH CH ),;OH (wherein g is approximately 12) 21 g. of50% active NaH in mineral oil 300 ml. p-dioxane (solvent) 100 g. allylbromide (excess).

In preparing the allyl ether, the reaction mixture was heated at 80 C.for 24 hours rather than held overnight at room temperature.

In the next stage of the synthesis, the following ingredientswere placedin a dry, 60-m1., glass vessel:

23 g. of the allyl ether (0.04 mole) 0.15 ml. t-butyl perbenzoate 6.2ml. Cl SiH (0.06 mole).

The vessel was sealed and placed in a steam bath overnight. Then theliquid product was heated under reduced pressure to remove unreactedtrichlorosilane. About 2.5

g. of unreacted Cl SiH was collected in a Dry-lice trap,

to water. A water-soluble product was formed which could be cured to aninsoluble cross-linked rubber on re moval of water and heating at 150 C.for ca. 30 minutes.

Example 3.Preparation of Monomer F p onsioH. 3-o-(om-onz oLwnnrsicn vThe preparation of this monomer was similar to that of Monomer D exceptthat the di-allyl ether of triethylene glycol was first prepared andfollowed by the addition of two moles of trichlorosilane.

In preparing the di-allyl ether the following chemicals were employed:

After addition of the allyl bromide, the slurry was heated with stirringovernight at 60 C. The salt was removed by filtration and the filtratedistilled. A crude product was obtained in a yield of 163 grams, b.p. C.at about 5 mm. Hg. Analysis thereof showed the desired vinyl absorptionbut also some residual OH which was due either to unreacted triethyleneglycol or monoallyl ether. Accordingly, the crude product was treatedwith increments of a high molecular weight (MW 600) aliphaticdi-isocyanate (General Mills DDI) to tie v up residual OH-containingproducts. The di-isocyanate was added slowly, and the product checkedfrom time to time until there was no evidence of free NCO in theproduct. The reaction mixture was then distilled under vacuum to givethe di-allyl ether product free from OH, b.p.ca. 145 C. at5 mm. Hg.

Addition of trichlorosilane to the diallyl ether was carried out asdescribed in the preparation of Monomers E and F, by adding 2 molarequivalents of HSiCl to the diallyl ether in the presence of t-butylperbenzoate catalyst.

Example 5.--Preparation of Monomer H 0 (3H, CHa-O-(CHrCHz-Oh-A-CH-Si013This monomer was prepared by first adding dropwise the rnonomethyl etherof diethylene glycol to a. two-fold excess of acryloyl chloride held at40 C. A nitrogen purge was maintained throughout the addition and for ahalf-hour after the addition had been completed. After this, excessacryloyl chloride was removed under vacuum and the acrylatc distilledunder vacuum to obtain an 80% yield, b.p. 7072-C. at 1.5 mm. Hg.

Trichlorosilane was added to the acrylate by heating together in asealed tube: 0.07 mols of the acrylate, 0.2

g. of 2,6-di-t-bi1tyl 'p-cresol (polymerization inhibitor), 12 ml. ofHSiCl and 0.2 ml. of a 0.00014 molar solution of H PtCl -6H Oisopropanol.

Example 6.Preparation of Copoly-mers Copolymers were generally preparedby the co-hydrolysis of a mixture of the monomers, either by adding theY mixture to water with vigorous stirring or, preferably, by

first dissolving the mixture in a solvent such as acetone, p-dioxane,tetrahydrofuran or other solvent which is partially to completelymiscible with water, then adding water to the monomer-solvent solution,and finally removing solvent under vacuum.

(A) An example follows for the copolymerization of Monomers A and D: Twoml. of Monomer A was mixed with 1 ml. of Monomer D, and the mixtureadded to 20 I The liquid polymer could be converted into an insoluble,

rubbery solid by heating. For example, heating at 150 1 C. for minutesconverted a thin layer of the liquid into a rubbery solid. A truecopolymer existed since a mixture of the homopolymer of A and thehomopolymer of D were incompatible and formed two insoluble layers onmixing.

A series of copolymers were prepared as described in paragraph (A)above:

Polymer I, derived from Monomers A and D, contains recurrent units ofthe structures Polymer II, derived from Monomers A and D andtrichlorosilane, contains recurrent units of the structures shown inFormulas VIII and IX plus HSiO Polymer III, derived from Monomers A andE, contains recurrent units of the structure shown in Formula VIII plusCH O(CH -CH O) (CH SiO wherein g is approximately 12.

Polymer IV, derived from Monomers A and F, contains recurrent units ofthe structure shown in Formula VII-I plus Polymer V, derived fromMonomers A, B, and G, contains recurrent units of the structure shown inFormula VIII plus (CF CF-O--(CH Si(QH )O and 0 (wherein g isapproximately 12).

Polymer VI, derived from Monomers A, C, and H, contains recurrent unitsof the structure shown in Formula VIII plus and Example 7.-FabricTreatment The fabrics used in the treatments were a tri-blend ofwool/cotton/nylon and a tri-blend of wool/rayon/polyester.

Treatment of the fabrics with the copolymers of the invention werecarried out by immersing the fabrics in a solution of the copolymer intrichlorotrifiuoroethane or l,3-bis-trifiuoromethyl-benzene. In somecases the copolymer was applied as an aqueous emulsion. After immersionin the solution or emulsion, the fabrics were run through squeeze rollsto obtain a 50-60% wet pick-up. The treated fabrics were then air-driedand cured in an oven at 150 C. for 10-20 minutes. After removal from theoven and cooling to room temperature, the products were tested for oilrepellency and for soil release as previously described. In someinstances the fabrics, prior to application of the copolymers, weretreated with dimethylol dihydroxyethylene urea (DMDEU) in order toimpart durable press properties and to examine the eflectiveness of thecopolymers in the presence of this conventional finishing agent. Thedurable press fabrics were prepared as follows: A 20% aqueous solutionof DMDEU containing approximately 0.5% Zn(NO catalyst and 0.2% of anon-ionic detergent was prepared. Fabrics were immersed in thissolution, then squeezed to a wet pick-up of 4050%. The fabric swatcheswere air-dried, pressed for one minute on a high-heat (350 F.) press andthen cured in an oven at 325 F. for 15 minutes.

The following table summarizes the results of fabric treatment with thevarious copolymers described in Example 6.

In certain cases, the copolymers were applied as aqueous emulsions. Atypical example of emulsification follows: Ten grams of copolymer IIIwas dissolved in 10 mi. of benzotrifluoride. To this was added 50 mg. ofa commercial wetting agent (Igepal CO-530, a nonylphenoxypolyoxyethylene glycol containing 6 ethyleneoxy groups per molecule).This solution was added slowly to 80 ml. of water containing 50 mg. of acommercial wetting agent (Igepal CO-7l0, a nonylphenoxy polyoxyethyleneglycol containing 12 ethyleneoxy groups per molecule) which was beingstirred in a high-speed blender. The emulsion which resulted could beused as such or diluted further with water.

TABULATION OF RESULTS OF FABRIC TREATMENT Cure con- Oil repellencyCopolymer Code No. and ditions, Stain concentration in solution or temp.(3/ Before After release emulsion time min. Fabric washing washingrating I, 2% solution /10 W/C/N and DMDEU...;. 3 2 5 Do 110/20 o 3 2 5II, 2% solution..- 110/20 W/R/P and DMDEU 5 4 5 III 3% emulsion /15 W/O3 2 5 IV, 3% solution 2 2 4 V, 1% solution... W/R/P 2 1 4 VI, 3%solution W/R/P and DMDEU 6 5 4 one W/O/N and DMDEU 0 0 2. 5 Dn /C/N 0 0a. 0

Do W/R/P 0 0 2. 0

Do W/R/P and DMDEU 0 0 1.0

'W/C/N =wool/cotton/nylon;W/R/P=wool/rayon/polyester; DMDEU=dimethyloldihydroxyethylene urea:

Hereinabove we have described a series of hydrophilic monomers. Thesecompounds may be formed .into homopolymers' by applying conventionalhydrolytic polymerization techniquessuch as those described above. Wehave observed that these homopolymers may be applied tofibrous'materials to improve their-soiljrelease properties,

however, the results are not as good as" those-obtained by applicationof the aforesaid copolymers with olephobic monomers. Of course, thehomopolymers do not provide any resistance to oily staining. Takingthese items into consideration, the homopolymers .of the hydrophilic.monomers are useful in situations where it is desired to render afibrous material hyrophilic. They also exert a softening effect on thesubstrate so that they are also useful for that purpose. In a practiceof this aspect of the invention, the homopolymers are applied to thefibrous substrate in the same manner as described above in connectionWith the copolymers, and subjected to the same curing step. Thefollowing examples illustrate the preparation of the homopolymers andtheir application to textile matfl'ials.

Example 8.--Polymerization of Monomer D Example 9.-Polymerization ofMonomer E This monomer was polymerized by adding 1 ml. of water to 5 ml.of the monomer dissolved in 25 m1. of tetrahydrofuran. After stirring atroom temperature for 1 hour, the solvent was removed under vacuum,leaving a thick water-soluble fluid polymer. This product could also beconverted to a crosslinked, rubbery, water-insoluble film by heatingabove 100 C.

Example 10.Treatment of Textile The textile used in the following testswas a tri-blend fabric of wool/rayon/polyester which had been given adurable press treatment as follows: The fabric was immersed in a 20%aqueous solution of dimethylol dihydroxyethylene urea containing 0.5%zinc nitrate catalyst and 0.2% of a non-ionic detergent. Following thisthe fabric was squeezed in a pad roll to a 60% wet pick-up, air-dried,pressed for 1 minute in a hot head press (350 F.), then oven-cured at325 F. for minutes.

An aqueous solution of polymerized Monomer E was prepared by adding 5ml. of the monomer to 95 ml. of

water. After the addition, the solution was brought to 5 neutrality byadding 1 N sodium hydroxide. A swatch of the fabric was immersed in thissolution, squeezed to 60% wet pick-up, air-dried, and cured in an ovenat 300 F. for 5 minutes.

The treated fabric and, as a control, a swatch of fabric which had notbeen treated with the polymer were then tested for stain releasability.To this end, the swatches were stained with mineral oil, washed, andrated for Residual stain is rated on a scale from 5 to 1 by comparison ia s a ds i r lsass rrpl sawhic di whereas the control had a rating of,l. 5.

.- m ts of s s g m s v. '3.

stain release according to AATCC Test Method 1304969.

plays a graduated series of sftaiii Thehig est nu be ,iridicates'complete stain'rem indicates virtually. no stain remo Theresults .olitai rted', were;ja foll'o treated with the polymer had astain 're lease' r in A wherein:

1 a each R is a member of-the group, consisting of-hyjdrogen, monovalenthydfoearbon radicals, and monovalent halo-hydrocarbon radicals, 1.; fAlk is an alkylene radicalacontaining-Z: to 6 carbon atoms, x is aninteger from 2 to 10.0, c is an integer from 010.2, 1 v: d is an integerfrom 1 to 3, the sum of c and d is 3,- c is an integer from 0 to 2, d isan integer from 1 to 3, and the sum of c and d is 3.. v l V 2. Asiloxane homopolymer which contains recurring units of the structure"CH: Re

each R is a member of the group consisting of hydrogen, monovalenthydrocarbon radicals," and "monovalent halo-hydrocarbon radical's,'

Alk is an alkylene radical containing 2 to 6. carbon atoms, r

x is an integer from 2 to 100,

c is an integer from 0 to 2,

d is an integer from Ito 3., M p W the sumofcanddis 3,

c is an integer from 0 to 2,

d is an integer from 1 to 3, and

the sum of c and a" is 3. i

References Cited UNITED STATES PATENTS 3,461,148 8/1969 Tamura er al.260-4482 B X 3,657,305 4/1972 Morehouse 260-4482 B 2,868,824

